Manufacture of water-insoluble azo dyestuffs



Patented Oct. 11, 1932 may be represente UNITED s'r Tas PATENT OFFICEimam omnrnnnnno AND wrnnnnx NEELMEIER, or LnvEizxnsEN oN-rnE-anmn,

AND JosEr mum, or wmsnoar-on-mn-anmn, onmmnr, nssrenoas EBAL ANILINEWORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE MANUFACTUREOF WATER-INSOLUIBLE AZO DYESTUFFS Ho Drawing. Application filed April25, 1989, Serial No 858,182, and in Germany lay 7,1928;

. The present invention relates to a process of preparingwater-insoluble azo dyestufl's;

According to this invention, water-insoluble azodyestuifs are preparedeither in substance, or on the fiber according to the dyeing or printingprocess by using in said processes the condensation products ofdiazocompounds, tetrazocompounds or diazo-azocompounds, containing nosulfonic acid and no carboxylic acid groups, with certain secondaryamines. These condensation prod-. ucts used for the by the generalformula:

wherein R stands for the residue of a diazotization component suitablefor producing azodyestufis, which may be substituted except by asulfonic acidor carboxylic acid group, and which may contain one or moreazo grou s, R and R stand eitherfor the same or ifierent residues of thegroup comprising alkyl, phenyl and, benzyl groups, at

' least one of the residues R and R being substituted by a substituentinducing solu- "bilit in water, such as the -COOH-, -SO H- or .SOH-groups, and n stands for one of the numbers one and two.

' These condensation products are obtainable by diazotizing ortetrazotizing in the usual manner with hydrochloric acid or sulfuricacid and sodium nitrite an "aminoor diamino-compound containing, nosulfonic I said solution containing an acid binding agent, such assodium or potassium carbonate or bicarbonate, favorably at temperaturesbetween about 0 C. and +10 C. The new condensation products separate ina crystal- (purpose of our invention line form during the reaction, orthe separation is completed by salting out the new products. The aregenerally yellowish to brownish colore crystallizing substances, andpossess the important property of undergoing no decomposition in neutralor alkaline aqueous solution, while they are decomposed quantltat velyinto their components by the action of diluted mineral acids or acidmineral acid salts or strong organic acids, such as formic acid, aceticacid or oxalic acid.

According to the invention, azo d estuffs in substance are prepared bydisso ving 'a condensation product of the above identified 1 generalformula in water and adding thereto an about equivalent quantity of anycoupling component suitable for producing azodye stufl's containing nosulfonic acid and no corboxylic acid group in an aqueous solution. Thenthe mixture is acidified by a strong organic acid, such as formic acid,acetic acid or oxalic acid, until a 510% acid solution has formed. Theformation of the dyestufi' begins immediately and can be accelerated byslowly heating, say to about 5060 C If the solution is acidified with amineral acid or an acid mineral acid salt, for example hydrochloric acidor sodium bisulfate, the decomposition of the condensation productproceeds more quickly; but in this case the free mineral acid must beneutralized, for

example by the addition of soda or sodium acetate for efiecting thecoupling.-

Otherwise the dyestufl may be prepared (by introducing the aqueoussolution of a coupling component containing no sulfonic acid and-nocarboxylic acid group into the aqueous solution of the condensationproduct to which an acid previously has been added; this method ofpreparing the dyestufl.

is equivalent to that described above.

In preparing the dyestufl' on the fiber, es-

pecially on cotton, the material to be dyed is impregnated with agrounding liquor containing a coupling component which is notsubstituted by a carboxylic or sulfonic acid group, for example, a2.3-l1ydroXy-naphthoic acid arylide or a naphthol, centrifuged,

' wrun and developed for solving about 3 to about grams of the aboveidentified condensation product in 1 liter of water and adding theretothe necessary quantity of an acid, preferably formic acid or aceticacid, generally to com of the concentrated acid being suflicient for 1liter. Into this solution there is introduced the cotton impregnatedwith the coupling component. the bath is advantageously slowly heated toabout 50-60 C., and when the diazo compound can no more be detected, thecotton is rinsed, soaped at the boil, rinsed and dried.

Our new process is favorably used for preparing dyeings on the fiberaccording to the printing process. The printing paste used c or thispurpose is prepared by mixing together about equivalent quantities of acondensation product as above identified and a coupling component,containing no sulfonic and no carboxylic acid group, especiall a 2.3-

hydroxy-naphthoic acid arylide, ad ing to the mixture caustic soda lyein a quantity sufiicient for dissolving the components and making up themixture to a printing paste in the usual manner by adding thereto athickening agent, such as starch or gum tragacanth and the necessaryquantity of water, and if desired, Turkey red oil. The fiber is printedwith this printing paste in the usual manner, then it is dried andtreated for a short time, say for about 20 seconds, in a bath containingan acid and if desired a suitable salt, such as Glaubers salt, sodiumchloride or the like. Generally we carry out the developmg process bypassing the printed cotton through a bath containing about 540% offormic acid or acetic acid and 10% of Glaubers, salt at an elevated temrature, say at temperatures between 50 an 90 C.

The invention is illustrated by the following examples, but is notrestricted thereto:

Example 1.-5.9 grams of the condensation product obtained fromdiazotized 3-nitro-4- amino-l-methylbenzene and sodium2-ethylcamino-1-methylbenzene-4-sulfonate are dissolved in warm waterand an alkaline solu tion of 3 grams of aceto acetic acid anilide isadded. On the gradual addition of acetic acid formation of the dyestufloccurs, which can be accelerated by raisin the temperature. When thecondensation prod ct can no longer be detected the yellow dyestufi ofthe formula:

of cold water. 20 grams of acetic acid and 5 grams of alum are thenadded and cotton previously impregnated in the customary manner with2.3-hydroxy-naphthoic acid-4'- chloro-2'toludide is .developed with thissolution. Rapid formation of the dyestufi of the formula:

on the fiber and the. reaction is completed gradually raising thetemperature to b about 60 C. After rinsing and soaping at the boilinpoint a clear red is obtained.

Ewamp e 3.6 ams of the condensation product obtaine from diazotized paraaminoazotoluene and one molecule of potassium dibenzylaminodisulfonateare dissolved in 1000 ccm of water at ordinary temperature and 30 gramsof acetic acid are added to the clear solution. At room temperature thesplittin up of the diazo compound only occurs slow A skein of cottonpreviously impregnate with 2.3-hydroxynaphthoic acid a-naphthylamide isthen introduced into the solution and heated to about 50-60 C. whilstcontinuously moving the skein. When the decomposable diazo compound canno longer be detected in the solution the skein is rinsed and soaped.The cotton is thus dyed a deep Bordeaux red with the dyestufi of theformula:

. two molecules of potassium N-ethyl-o-tolui- The splitting u of thediazo condensation product can also carried out with smaller quantitiesof organic acids provided it takes place in the presence of only alittle water.

By replacing the condensation product in this example by the product ofthe action of one molecule of tetrazotized dianisidine anddine-p-sulfonate, a dark blue is obtained.

E mample 4.-A solution of the condensation product obtained from'diazotized 4- chIoro-Q-amino-l-methylbenzene and sarcosine is mixed inthe molecular proportion with a solution of 2.3-hydroxynaphthoic acid-2'-toluidide in the calculated quantity of di lute caustic soda, and thewhole is evaporated to dryness under reduced pressure. grams liter aboutbluish red is o tained with the dyestufl' of the formula:

of the pale yellowish colored powder thus obtained are made into a pastewith a little Turkey red oil and mixed with starch tragacanth thickeningagent and water to the extent that the total weight of the finishedprinting paste amounts to 100 grams. The

no comer? CQNHQH H.

material is printed, dried, steamed and developed at about C. in abathcontaining 50 grams of formic acid and grams of sodium sulfate perliter. In this manner a clear red is obtained with the dyestufi of theformula: I

on; no I Co-NHQ N=N CH:

Ewample 5.--5.6 grams of potassium '2- methyl-- nitrobenzene-azo Nethylaminobenzene-3-sulfonate are finely powdered together with 6 gramsof the sodium salt of 2.3-hydroxynaphthoic acid-2-toluidide and themixture is worked up with a neutral thickener to 100 grams of printingpaste. The goods are printed, dried and the dyeing is developed in a'hotbath containing per rams of acetic acid. A full I no 00.1 1119 N=N 0H1om on,

Instead of the compounds mentioned,

other couplin components commonly used for the manu acture of azo destuflscan be employed, such as for examp e, B-naphthola-naphtholderivatives coupling 1n the arylides, 1:3- ydroxyquinolines and thelike. 4

compound, obtainable from diazotized 1- amino 2.5 diethoxy4-benzoylaminobenzene and sarcosine is dissolved with 1/200 mol of2.3-hydroxynaphthoic acid-2-toluidide in about 20 com of'water withabout 1.5 ccm of caustic soda (30%) and 3 com of Turkey red oil and thissolution is made up to 100 grams with a tragacanth thickening agent.

This printing paste is then printed on to the fabric, dried anddeveloped by once passing through approximately 5% acetic acid at about80 C. A blue is obtained which by subsequent soaping at the boilacquires a beautiful reenish shade. the following formula:

Example 7.On taking 1/200 mol of the diazoamino compound, obtainablefrom diazotized 1-amino-4-benzoylamino-2-methoxy- 5-methylbenzene andsarcosine and 1/200 mol of 2.3-hydroxy naphthoic acid anilide andproceeding as described in Example 6, a clear bluish violet is obtainedwith the dyestulf ofthe formula:

OH; HO ooNHO O CONHQN=N CH; I

' is'made up with the necessary quantity of thickening agent and water.After the printing the fabric ishung or steamed and the dyeing developedby treatment with a dilute organic acid, such as for example, 5%-

acetic acid or formic acid. The fabric is then rinsed and soaped at theboil. In this ortho-positiongyrazolones, diacylacetic acid Example6'.1/200 mol of the diazoamino The dyestufi has manniar. a deep black isobtained with the dyestufi of the formula:

H0 O0.NK

, 0.0m W MQH .CH:

Example .9.-40 grams of the condensation product obtainable from one molof tetrazo Example 10.By dissolving a mixture of 1/100 mol of thediazoamino compound obtainable from diazotized 4-chloro-2-toluidine andsa'rcosine and 1/100 mol of the diaceto acetic acid toluididc by theaddition of a little caustic soda lye and Turkey red oil in about 200com. of water and working after the addition of the thickener in ananalogous manner to that described in the Examples 6 and 7, a clearyellow is obtained with the dyestufi of'the formula:

CHI

a, 40 grams of Turkey red oil' Cl N=NC CO-NH NH-OO- 11430-011: H:

taining 5% formic acid and 10% sodium fo'rmate. Then the cotton isrinsed, boiled at ble azo dyestuffs comprising reacting with an acidreacting compound of the group consisting of mineral acids,water-soluble acid mineral acid salts and strong organic acids, upon amixture of any coupling component suitable for producing azodyestuflscontaining no sulfonic acid and no carboxylic acid group,

HN.CO on no 00 NH #QQM .cm .om

and a compound of the following formula:

wherein R stands for the residue of a diazotization component suitablefor producing azodyestuffs containing no sulfonic acid and no carboxylicacid group and which may contain an azo group, R and R stand forsubstituents of the group consisting of alkyl, the phenyl and benzylseries, at least one of which is substituted by a substituent of thegroup consisting of the -COOH-, -SO H- and O.SO H- I groups, and nstands for one of the numbers one and two.

2. The process of preparing water-insoluble azo dyestuffs comprisingreacting with an acid reacting compound of the group consisting ofmineral acids, water-soluble acid mmeral acidsalts and strong organicacids, upon a mixture of any coupling component suitable for producingazodyestufis containing no sulno carboxylic acid v fonic acid and nocarboxylic acid group and a compound of the following formula;

wherein R stands for the residue of a diazotization component suitablefor producing azodyestufls containingv no sulfonic acid and nocarboxylicacid group and which may contain an azo group, R and R stand for alkylgroups, at least one of which is substituted by a carboxylic acid group,and 1 stands for one of the numbers one and two.

3. The process of preparing water-insoluble azo dyestufi's comprisingreacting with an acid reacting compound of the group consisting ofmineral acids, water-soluble acid mineral acid salts and strong organicacids; upon a mixture of any coupling component suitable for producingazodyestufis containing no sulfonic acid and no carboxylic acid group,and a compound of the following formula:

wherein R stands for the residue of a diazotization component suitablefor producing azodyestufis containing no sulfonic acid and group andwhich may contain an azo group.

In testimony w ereof we have hereunto set our hands.

EUGEN GLIETENBERG. WILI-IELM NEELMEIER. JGSEF' HALLER.

